JP2000302944A - Thermosetting phenol resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting phenol resin composition and a molding material scarcely generating ammonia or an amine-based gas at the time of molding. SOLUTION: This composition is obtained by compounding 100 pts.wt. of a thermosetting phenol resin with 1-100 pts.wt. of a phosphoric acid compound, 0-30 pts.wt. of a sulfuric salt and 0-30 pts.wt. of titanium dioxide. The molded material is prepared by compounding the composition with a curing agent, a substrate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting phenolic resin composition and a molding material using the same, which reduces ammonia and amine gas generated during molding and the like.
The odor can be reduced.

[0002]

2. Description of the Related Art In a thermosetting phenol resin, especially a novolak type resin, hexamethylenetetramine is used as a curing agent, so that a relatively large amount of ammonia and amine-based gas is generated at the time of molding. I have. Even when a resol type resin does not use a curing agent, these gases may be generated due to the influence of the remaining base catalyst. Techniques for suppressing the generation of ammonia and amine-based gases include a method in which ferrous sulfate is mixed with a thermosetting phenol resin (Japanese Patent Application Laid-Open No. Hei 1-306602), a method in which iron chloride or iron sulfate is mixed. (Patent No. 26118
No. 09 publication). However, these prior arts have a drawback that the effect of suppressing ammonia and amine-based gases is insufficient.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to reduce the amount of ammonia and amine gases generated during molding of a thermosetting phenolic resin to a level at which no practical problem occurs.

[0004]

This problem is solved by blending a thermosetting phenolic resin with a phosphoric acid-containing composition or phosphate, and, if necessary, a sulfate and titanium dioxide.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The thermosetting phenolic resin in the present invention may be either a resol type resin or a novolak type resin, or a mixture thereof. The resole type resin is obtained by mixing a phenol (P) and an aldehyde (F) in a molar ratio (F / P).
= 1 or more, obtained by reacting in the presence of a base catalyst such as ammonia, hydroxide, amines such as hexamine.

[0006] The novolak type resin comprises a phenol (P) and an aldehyde (F) in a molar ratio (F / P) =
It is obtained by reacting at 1 or less in the presence of an acid catalyst such as oxalic acid, hydrochloric acid, sulfuric acid and the like. As the phenols (P), those having one or more phenolic hydroxyl groups in the molecule are used, and specifically, phenol, cresol,
Xylenol, nonylphenyl, resorcinol, catechol, bisphenol A, bisphenol F, and the like may be used alone or in a mixture of two or more, but not limited thereto.

The aldehydes (F) include formaldehyde, paraformaldehyde, glyoxal,
A single or a mixture of two or more of acetaldehyde, butyraldehyde, furfural and the like are used, but are not limited thereto. The method for producing these thermosetting phenolic resins is not particularly limited, and commercially available phenolic resins produced by conventional production methods can be used as they are.

The phosphoric acid-containing composition or phosphate (hereinafter abbreviated as a phosphoric acid compound) used in the present invention includes potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, and phosphoric acid. Sodium dihydrogen, disodium hydrogen phosphate, trisodium phosphate and the like and hydrates thereof,
Phosphorus fertilizer (fused phosphorous fertilizer), lime superphosphate, heavy burnt phosphorus, heavy superphosphate lime, advanced chemical fertilizers and phosphoric acid-containing fertilizers not covered by existing chemicals, and ordinary chemical fertilizers are used. Preferably fused phosphate fertilizer (fused magnesium phosphate fertilizer),
Superphosphate and heavy superphosphate are used, and the greater the phosphoric acid content, the greater the effect.

The amount of the phosphoric acid compound is 1 to 100 parts (parts by weight, hereinafter the same) of the thermosetting phenol resin.
100 parts, preferably 1 to 50 parts, and more preferably 1 to 30 parts. If less than 1 part, the effect of suppressing gas cannot be obtained, and if it exceeds 100 parts, the mechanical strength, chemical resistance, etc. of the molded product. Of various properties are deteriorated.

As the sulfate used in the present invention, salts which are solid at room temperature such as potassium sulfate, sodium sulfate, calcium sulfate, barium sulfate, zinc sulfate, aluminum sulfate and ammonium ammonium sulfate are used. Salts of strong acids are good, and calcium sulfate, barium sulfate, zinc sulfate, and aluminum sulfate are used.

The amount of the sulfate is from 0 to 30 parts, preferably from 0 to 2 parts, per 100 parts of the thermosetting phenol resin.
0 parts, more preferably 0 to 10 parts. When the amount exceeds 30 parts, various physical properties such as mechanical strength and chemical resistance of the molded article are reduced. Further, the sulfate is not necessarily required to be blended if a sufficient gas suppressing effect can be obtained by blending only the phosphoric acid compound.

The titanium dioxide used in the present invention may be either rutile type or anatase type, but is preferably rutile type. The blending amount of titanium dioxide is 0 to 30 parts, preferably 0 to 20 parts, more preferably 0 to 10 parts with respect to 100 parts of the thermosetting phenol resin.
Exceeding the part similarly deteriorates various properties of the molded article. In addition, this titanium dioxide is not an essential component, and may not be required in some cases.

The thermosetting phenolic resin composition of the present invention may further contain, if necessary, a releasing agent, a coloring agent, a filler, a silane coupling agent, a twist-resistant agent, a modifier, a modified resin, and the like. be able to. As the filler, calcium carbonate, talc, aluminum hydroxide, clay, mica, shirasu, pearlite, silica and the like are used.

The thermosetting phenolic resin molding material of the present invention comprises the above-mentioned thermosetting phenolic resin composition as an essential component, a reinforcing material (base material) and, if necessary, a curing agent,
It contains a lubricant and the like. Reinforcing materials include wood fibers, pulp, cotton, anti-hair,
Organic fibers such as hemp and chemical fibers, inorganic fibers such as glass fiber, glass wool, rock fiber, rock wool and carbon fiber, and powdered fillers such as wood flour (cellulosin), pulp powder, and mica are used.

[0015] The curing agent is compounded when a novolak type resin is used, and hexamethylenetetramine is used. The compounding amount is 2 to 100 parts of the resin.
It is about 25 parts. As the lubricant, metal soap such as calcium stearate is used. The compounding amount of the reinforcing material is 1.5 to 1 part of the thermosetting phenol resin composition.
About 100 parts.

The production of the thermosetting phenolic resin molding material of the present invention is the same as the conventional thermosetting phenolic resin molding material, and the conventional steps such as kneading and pulverization can be applied as they are.

In such a thermosetting phenolic resin molding material, since a phosphoric acid compound is contained in the composition, ammonia, amine-based gas generated from a curing agent or the like during molding and curing of the molding material is used. Is captured. That is, the condensed water generated when the phenolic resin is cured reacts with the phosphoric acid compound to form phosphoric acid, and the phosphoric acid undergoes a neutralization reaction with the generated ammonia, trimethylamine, etc., thereby capturing the ammonia and the amine-based gas . Further, the phosphoric acid compound similarly captures ammonia and amine-based gas generated by a curing reaction that gradually proceeds in the long term.

In the case of further containing a sulfate, the sulfate reacts with the condensed water to form sulfuric acid, and the sulfuric acid undergoes a neutralization reaction with ammonia and an amine-based gas. In addition, if titanium dioxide is contained, the titanium dioxide physically absorbs these gases generated gradually with time after curing, and the active oxygen generated from the titanium dioxide decomposes unreacted substances and low molecular compounds. .

By these actions, the generation of ammonia and amine-based gas from the molded article after the molding and curing is largely suppressed, and the odor is not generated. Further, these gases generated continuously and with time after molding are also trapped, and do not emit an off-flavor after shipping the molded article. Furthermore, the phosphoric acid compound and the sulfate also act as an acid catalyst during the curing reaction,
It also exerts the function of accelerating the curing reaction.

Hereinafter, specific examples will be described. Raw material phenolic resin A is a resole type powdered phenolic resin, and phenolic resin B is hexamethylenetetramine.
A novolak-type powdery phenol resin to which weight% was added, and an equivalent mixture (weight ratio) of resin A and resin B as phenol resin C were prepared.

(Examples 1 to 3) Five parts of aluminum sulfate and five parts of lime heavy perphosphate were added to 100 parts of each of resins A, B and C.
The parts were uniformly mixed and pulverized to obtain a resin composition. 65 parts of absorbent cotton was added to 35 parts of the resin composition, and the mixture was uniformly mixed and defibrated to form a forming mat.
by thermal pressure forming m ^2, and the thickness of 2.5 mm, density 0.6 g /
A molded plate of cm ³ was obtained.

Comparative Examples 1 to 3 Resins A, B and C
Without adding aluminum sulfate and lime heavy perphosphate
Then, the same operation as in Examples 1 to 3 was performed to obtain a thickness of 2.5 m.
m, density 0.6 g / cm ^ThreeWas obtained. (Measurement) These six types of molded plates were each 40 mm wide and long.
Cut into 70mm, put in a 4 liter can, sealed and 8
After heating at 0 ° C. for 1 hour, the mixture was cooled at room temperature for 20 minutes. Inside the can
Phenol, formaldehyde,
Kitakawa-style detector tube (Gastec)
Phenol: No. 60, formaldehyde: N
o. 91 L, ammonia: No. 3 L, amine gas:
No. 180). Examples 1 to 3 and Comparative Example 1
Tables 1 to 3 show the results.

(Examples 4 to 11) and (Comparative Example 4) Resin D and noblerac type resin B having an addition amount of hexamethylenetetramine of 7% by weight were used. What was made into the weight% was prepared as resin E. Table 1 for Resin D and Resin E
Aluminum sulfate, lime superphosphate, lime heavy phosphate, and titanium dioxide were blended at the blending ratios shown in the table, and a molded plate was produced in the same manner as in the example, and phenol, formaldehyde, ammonia, and amine-based gas were similarly produced. Was measured. Table 1 shows the results of Examples 4 to 11 and Comparative Example 4.

[0024]

[Table 1]

Table 1 shows that the thermosetting phenolic resin composition of the present invention generates less ammonia and amine gas than the conventional one.

(Examples 12 to 18) and (Comparative Examples 5 to 6) The above resins D and E were mixed with aluminum sulfate, lime perphosphate, and lime perphosphate in the composition shown in Table 2.
A resin composition was prepared by blending titanium dioxide and calcium carbonate. 65 parts of anti-hair are added to 35 parts of the resin composition, uniformly mixed and defibrated to form a forming mat, and the forming mat is heated at a temperature of 220 ° C. for a time of 60 seconds at a pressure of 2
The formed felt was formed under heat and pressure at 5 kgf / cm ² to have a thickness of 2.5 mm and a density of 0.6 g / cm ³ .

With respect to the obtained molded felt, the amount of generated amine-based gas and the bending strength were measured immediately after molding and one month after molding. The measurement of the amine-based gas is the same as in the previous embodiment. Table 2 shows the results.

[0028]

[Table 2]

From the results shown in Table 2, it can be seen that the thermosetting phenolic resin composition of the present invention generates little amine gas not only immediately after molding but also after one month, and there is no decrease in bending strength. . On the other hand, in the case of adding calcium carbonate, although the effect of suppressing the amine-based gas is slightly obtained, the bending strength is greatly reduced.

[0030]

As described above, according to the thermosetting phenolic resin composition and the molding material of the present invention, the amount of ammonia and amine gas generated during molding and curing can be greatly reduced. Is effective for novolak-type phenolic resins using as a curing agent. Further, the strength of the molded article does not decrease over time, and both ammonia and amine-based gas continuously generated after molding can be reduced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuhiro Ogura 700 Shukudaidaicho, Takasaki City, Gunma Prefecture Inside Gunei Chemical Industry Co., Ltd. (72) Mayumi Yanai 700 Shukudaitorimachi Takasaki City, Gunma Prefecture Gunei Chemical Industrial Co., Ltd. In-house F term (reference) 4J002 CC031 DE138 DG047 DH036

Claims (2)

[Claims] 1. A 100% by weight of a thermosetting phenol resin is mixed with 1 to 100 parts by weight of a phosphoric acid-containing composition or a phosphate, 0 to 30 parts by weight of a sulfate, and 0 to 30 parts by weight of titanium dioxide. A thermosetting phenolic resin composition comprising: 2. A thermosetting phenolic resin molding material comprising the thermosetting phenolic resin composition according to claim 1.